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bi 't. 3% Kiri-Litur- ZOE UH 3,303,136 Patented Feb. 7, 1967 3 303 136ing a soiled tile into quarters. One of the soiled quarters i was washedin a standard manner with solution (1). DETERGENT COMPOSITIONS Thesecond quarter was washed with solution (2). The

Willard M. Bright, Ridgewood, NJ., assignor to Lever third quarter waswashed with solution (3). The fourth 33%; Company New York corpomhon of6 quarter was kept as an unwashed control. tile was No Drawing Filed Feb26, 1963, Ser. No 261,193 used for each series of three solutionsevaluat ng a given 6 (313mm (CL 252.133) sulfonate. The washed tileswere inspected visually and ranked for cleanliness by a panel of threeobservers. The The present invention relates to detergentcomposifollowing hydrotropes were evaluated: sodium orthotions and toimprovements in the cleaning of hard sur- 10 xylenesulfonate, sodiummetaxylenesulfonate, potassium faces. More particularly, it pertains topolyphosphateparaxylenesulfonate, sodium toluenesulfonate, sodium arylsulfonate compositions having synergistic cleansingethylbenzenesulfonate, and sodium isopropylbenzenesulproperties. fonate.

Materials which aid in producing homogeneous liquids Details of the testfrom substances which are incompatible in aqueous media are known as y pShort chain alkyl y 5111- The details of soiling, washing and rankingfollow: fonates have been used to solubilize the longer chain s0iIing-The floor m used were 9 inches x 9 inches alkyl y 0f sulfonates andother Organic detergents in Armstrong Asphalt Tile, factory finished,Pattern D-900 the Presence of complex, inorganic p p Ivory Marble, /sinch gage. A layer of vacuum cleaner ever, it has 11m bun generallyIecOgniZcd that these dust (screened through 80 mesh to remove largerconventional hydrotropes also possess detergent properties sincecompositions containing polyphosphates and short chain alkyl arylsulfonates have always contained synthetic detergents to providesuitable detergent activity to the formulations. Specifically, it hasnot been recognized that products containing a polyphosphate and thesehydrotropic agents are particularly efiicacious in cleaning hardsurfaces such as tiles and other coverings for floors, walls and thelike.

It is an object of this invention to provide detergent compositionshaving synergistic cleansing characteristics.

Another object is to take advantage of the discovery that short chainalkyl aryl sulfonates contribute significantly to the detersiveproperties of formulations containing complex inorganic polyphosphates.

Still another object of the invention is to provide a means forefficiently cleansing hard surfaces.

It has now been found that certain sulfonates conventionally used ashydrotropes have enhanced tolerance for condensed phosphates and thatsuch polyphosphatesulfonate compositions exhibit synergistic propertiesin cleaning hard surfaces such as painted walls, floor tile and thelike.

The polyphosphate-sulfonate mixtures according to this particles) wasrubbed evenly over the surface with a cloth. Any excess loose dust wasshaken from the tile, and the area now soiled with adhering dust wascovered with three successive layers of liquid floor wax (this operationsimulated waxing a normally solid floor). Each layer of wax was allowedto dry in air before the next layer was applied.

Washing.The method of washing consisted of dipping a 3 inches x 4 inchesswatch of new clean white terry cloth into the detergent solution,squeezing excess liquid from the fabric and rubbing each soiled area ina standard manner for 30 seconds. The loosened soil-detergent mixturewas then wiped from the surface with a new clean 5 inches x 9 inchesWipette (an absorbent cellulose napkin).

Grading and ranking.The quarters of each tile were compared forcleanliness by a panel of three observers under standard daylightlighting conditions. The cleanest quarter was ranked 1, the nextcleanest 2, the next cleanest 3 and the least clean 4.

The results of tests performed on the solutions described above aretabulated below. The symbol TKPP designates tetrapotassiumpyrophosphate.

invention contain from about 40% to about 85% of at least onewater-soluble salt of a polyphosphate and from Cleanness g Quarter ashedabout 15% to about 60% of at least one water-soluble arylsulfonate. Theproportions are based on dry mixultanate Series tures of thesetwoingredients. The polyphosphates used s gig: g gg in thesecompositions include tetrapotassium and tetrao e ggg sodiumpyrophosphate, sodium and potassium tripolyphosphates and mixtures ofthese ingredients. The 5141; EAR which can be used include the alkalimetal and 3 2 1 4 ammonium salts of benzene sulfonate, ortho-, meta-,and Sodium meta-xylenewb ionate 3 2 1 4 para-xylene sulfonate andmixtures of these isomers, pgmssium pmqylenesul- 2 2V 1 4 onate.

toluene sulfonate, ethylbenzene sulfonate, n propyl and sodiumtoluenesulmnatem 3 2 2 z 1 4 isopropylbenzene sulfonate, etc. as well asvarious comsodium ethylbenzenesul binations of these materials. ggg ig 14 It is within the scope of the present disclosure that 110mm 3 2 1 4such additional ingredients as fillers, colorants, perfumes,

optical dyes, bleaches, and germicides may be added.

The following examples serve to illustrate'the present invention,without however, limiting the same thereto.

EXAMPLE 1 NOTE l.A ranking of is given to indicate the median when twodetergents are tied for two adjacent ranks. Thus, a ranking of "28/indicates that a tie occurred for 2 and 3 ranks and, l indicates gist aSe occurred for 1" and 2 ranks, i.e., "cleanest" and "next to eanes Itwas necessary to warm the sodium ortho-xylene-sulfonate solution, andthe solution of the sodium orthoxylenesulfonate-TKPP mixture to meltcrystals before use.

It was necessary also to warm the potassium paraxylenesulfonate solutionto melt the crystals. However, these crystals reformed as soon as thewarmed solution was touched to the cold tile. Crystals were not removedfrom the mixture of potassium para-xylenesulfonate and TKPP even withwarming, and when used this solution contained a small amount ofcrystals.

EXAMPLE 2 The following results were obtained using mixtures oftetrapotassium pyrophosphate (TKPP) and commercial sodiumxylenesulfonate (SXS) for cleaning a standard soiled wall surface. Fivesolutions of tetrapotassium pyrophosphate of varying concentrations wereeach used in combination with various concentrations of the sulfonate.Various percentage concentrations of tetrapotassium pyrophosphate inwater solutions, namely: 22.5%, 21.0%, 18.0% and were each tested with8.0%, 6.9%, 4.6% and 0% of sodium xylenesulfonate. For these tests, 0%of either tetrapotassium pyrophosphate or sulfonate was considered aconcentration level of that component.

A panel of white Walltex, 4 feet x 2 feet, was attached with tape to awooden table top. The surface was evenly soiled by application of amixture of screened vacuum cleaner dust, oildag (colloidal graphite andpetroleum oil) and cooking fat (bacon grease). An ordinary 9 inch paintroller was used in applying the soil evenly. The application of soil wasadjusted to bring the soiled reflectance to a level of 17% on the Hunterreflectometer equipped with a green filter. The Hunter reflectometer isstandardized so that the reflectance of a magnesium oxide block is 100%(green filter). For each run this test panel was divided into fifths,lengthwise, making five equal-sized rectangular test areas.

Washing of soiled areas.The washing of the soiled area was conducted atlevels of 22.5%. 21.0%, 18.0% and 0% TKPP in combination with 8.0%,6.9%, 4.6% and 0% of SXS. Solutions of each component identified bynumerals for tetrapotassium pyrophosphate and letters for sodiumxylenesulfonate were prepared so that equal weight portions of eachcomponent would give the desired mixtures.

Percent- Cone. of Prepared Solutions To illustrate-la called for equalweights of 1) 45% TKPP and (a) 16% SXS giving a resultant mixture (1a)of 22.5% TKPP and 8.0% SXS.

The washing scheme was as follows:

The above prepared solutions were used at room temperature in astandardized manner, 20 milliliters of solution placed in a inch watchglass. A clean white piece (3 inches x 4 inches) of new terrycloth wasdipped into the solution until the cloth became saturated. The fabricwas removed, squeezed between the fingers to remove excess moisture, andrubbed over the rectangular soiled Walltex test area for 30 seconds. Thedirt and detergent mixture left on the test area was removed byabsorption with an absorbent tissue. After drying, the reflectance ofthe tested area was determined in four locations.

When the test washings had been completed, the test area of 9.6 inches x2 feet was cut from the larger 2 feet x 4 feet panel of Walltex used foreach run. The resultant smaller swatch was easier to handle during thereflectance determinations on the Gardner color difference meter. Eachcleaned area was read four times along the longer central axis. Sincethere were four replicates for each 4 detergent, the reflectances shownin Table H are the averages of 16 readings for each detergent mixture.

TABLE 11 [Average reflectance of standard soiled Walltex panels afterwashing] Percent Sodium Xylenesulfonate Percent TKPP 22. 64. 9 64. T 64.0 52. 5 21. 64. 3 G3. 6 05. 5 55, 4 18. 61. 9 6i. 5 62. 0 4R. 9 0. 41. 442. 9 40. 7 37. 5

EXAMPLE 3 Additional tests were conducted using the same procedure asdescribed in Example 2 employing a 24% concentration of TKPP and a 13.8%concentration of SXS so that combining equal weights of the TKPPsolution with the SXS solution gave a mixture containing 12% TKPP and6.9% SXS. The following reflectances were observed.

TABLE III [Average reflectance of standard soiled Walltex panels afterwashing] Conc. Sodium Xylenesulionnte Cone. TKPP, Percent EXAMPLE 4Additional tests were conducted with a combination of 70% tetrapotassiumpyrophosphate and 30% tetrasodium pyrophosphate (TSPP) with ortho-,meta-, and paraxylene-sulfonates, and 50-50 mixtures of these isomers.

The following mixtures were tested:

TABLE IV [All percentages are by weight] Percent Percent PercentSolution Percent Percent Ortho- Meta' Parn- Number TKPP TSPP SXS SXS SS5Samples 1, 4, 6, 7, 8 and 9 contained crystals. These mixtures wereheated to 50 C. (122 F.) to dissolve the separated solid material andwere used at this temperature; the remaining solutions were used at roomtemperature F.).

Each soiled panel was divided into 5 test areas, as described in Example2. The test solutions were used in a random fashion until four replicatewashings had been made with each mixture. The standardized washingPercent Sodium Xylene Sultonate Comm. Grade.

method was used and the reflectances ot the cleaned areas weredetermined as follows:

TABLE V [Average reflectance of washed standard soiled panels] PercentPercent Percent Percent Percent Unadjusted Solution TKPP TSPP Ortho-Meta- Para- Reflectance SXS SXS SXS than those values obtained by addingthe adjusted reflectance for the sulfonate alone and those for the pyro-Adjusted Reflectance Nora-The reflectances were adjusted for the waterblank by cl a panel washed in water alone; thus, the adjusted figureshows solution, over and above that done by water.

These results indicate that solutions containing the tetra-phosphatemixture plus sulfonate (either a single isomer or mixed isomers) aresuperior to the combined results of solutions containing phosphatealone, or sulfonate alone.

EXAMPLE 5 Additional tests were conducted to determine the reflectancesobtained from mixtures of pyrophosphates alone, sulfonates alone, andsulfonate mixtures alone. The results are tabulated below:

TABLE VI [Average reflectance of washed test areas] subtracting thereflectance the cleaning done by the phosphate alone. This clearlydemonstrates the synergism of the present invention.

EXAMPLE 6 Further tests were performed on a series of mixtures todetermine their eflFectiveness in cleaning hard surfaces. The productswere evaluated as described in Example 2 by washing a Walltex boardsoiled in a standard manner. The reflectance of each swatch of the wallcovering was measured on the Gardner color dififerencc meter.

The mixtures received as solutions were used in the Percent PercentPercent Percent Percent Unadjusted Solution TKPP TSPP Ortho- Meta- Para-Reflectance SX S 5X S SX S Adjusted Reflectance tests as is withoutdilution. All solutions were heated to about 110 F. before use. PowderedProduct 6 was utilized by dissolving 32.5 grams of the mixture in 67.5ml. of distilled water. A washing temperature of 110 F. was maintainedin all tests.

TABLE VII [Composition oi products and reflectance of washed Walltexwith adjustment for reflectance oi water blank] Product Number Soln.

Percent Penta Sodium Tripolyphosphate Percent Penta PotassiumTripolyphosphate Percent Calgon"-Mainly Hexametaphosphate (NaPOa)a-Percent Ammonium Xylene Sulior Percent Tetra Potassium Pyrophosphate.

Percent Sodium Silicate Solids (SiO,:Nai0=2.0) Percent Perfumes PercentBlue Dye (Hastings S liy Blue") Percent Sodium Benzene Sullonate.

Percent Fluorescent Dye e Percent Potassium Dichloroisocyanurate.

Percent Sodium Metasilicate, Solids.

Percent Germicide 2. 77 Percent Water 69. 5 09. 5 69. 5 74. 0 36. 5 7.60 69. 5 100. 0 69. 5 Percent Total 100.00 100. 0 100.00 100. 0 100 100.00 100. 0 100. 0 100. 0 Average Reflectance of Washed Sw ColorDifference Meter 26. 9 30. 2 48. 7 31.1 57. 0 48. 7 54. 5 18.1 51. 1Average Reflectance Minus Water Blank, or ControL. 8. 8 12. l 30. 6 13.0 38. 9 30. 6 36. 4 0. 0

I 4-4'bis "-morphilino-fi" anilino-l",3,"-triazin-2-ylamino)-stilbene-2,2-disuiionic acid, Na salt.

b Approx. equal parts by weight oi 4,5-dibromoand3,4',5-tribromosa1lcylanilide.

It is seen from the above data that Product 4 containinghexametaphosphate is not within the scope of the invention since nosynergistic results are obtained. However, the pH of this product wasabout 5 while the pH of other formulations within the scope of theinvention was higher than 7, i.e., on the alkaline side. It will berecognized that the lack of synergism in Product 4 may be due to therelatively low pH and that this can be overcome by means well-known tothose skilled in the art.

Moreover, it is evident from Product 6 above that compositionscontaining the polyphosphate and sulfonate of the invention can bemarketed as dry powders and the ultimate consumer may add water beforeusing if desired.

Additives which do not materially alter the beneficial characteristicsof the mixtures of this invention may be incorporated as shown in theabove table. The amount of the additives should not exceed about 45%based on the weight of the dry ingredients. Thus, up to about 3% of agermicide and 3% of sodium silicate solids can be presem, as well as amaximum of about 10% of a chlorinereleasing bleaching agent. Other inertingredients up to the 45% maximum can be added.

The term Walltex as used in the above examples refers to a coated cottonfabric waterproof wall covering which may be applied with paste in muchthe same manner as wall paper.

It will occur to those skilled in the art that there are manymodifications to this invention as specifically described therein. It isintended to include all such modifications within the scope of theappended claims.

What is claimed is:

1. A composition consisting essentially of about 40% to about 85% of awater-soluble condensed, inorganic polyphosphate and from about to about60% of a water-soluble aryl sulfonate selected from the group consistingof benzenesulfonate, ortho-xylenesulfonate, metaxylenesulfonate,para-xylenesulfonate, toluenesulfonate, ethylbenzenesulfonate,n-propylbenzenesulfonate, isopropylbcnzenesulfonate and mixturesthereof, the proportions being based on the weight of the dryingredients, said composition providing an alkaline reaction in aqueoussolution.

2. A composition consisting essentially of about 40% to about 85% of awater-soluble condensed, inorganic polyphosphate, about 15% to about 60%of a watersoluble aryl sulfonate selected from the group consisting ofbenzenesulfonate, ortho-xylenesulfonate, meta-xylenesulfonate,para-xylene sulfonate, toluenesulfonate, ethylbenzenesulfonate,npropylbenzenesulfonate, isopropylbenzenesulfonate and mixtures thereof,up to about 10% of a chlorine-releasing agent, up to about 3% of agermicide and up to about 3% of a sodium silicate, the proportions beingbased on the weight of the dry ingredients, said composition providingan alkaline reaction in aqueous solution.

3. An aqueous dispersion of the composition recited in claim 1.

4. An aqueous dispersion of the composition recited inclaim 2.

5. A method which comprises cleansing a hard surface by contactingtherewith a composition consisting essentially of about 40% to about 85%of a condensed inorganic water-soluble polyphosphate and from about 15%to about of a water-soluble aryl sulfonate selected from the groupconsisting of benzenesulfonate, ortho-xylenesulfonate,meta-xylenesulfonate, para-xylenesulfonate, toluenesulfonate,ethylbenzenesulfonate, n-propylbenzenesulfonate,isopropylbenzenesulfonate and mixtures thereof, the proportions beingbased on the weight of the dry ingredients, said composition providingan alkaline reaction in aqueous solution.

6. A method which comprises cleansing a hard surface by contactingtherewith a composition consisting essentially of about 40% to about ofa condensed, inorganic water-soluble polyphosphate, from about 15% toabout 60% of a water-soluble aryl sulfonate selected from the groupconsisting of benzenesulfonate, ortho-xylenesulfonate,meta-xylenesulfonate, para-xylenesulfonate, toluenesulfonate,ethylbenzenesulfonate, n-propylbenzenesulfonate,isopropylbenzenesulfonate and mixtures thereof, up to about 10% of achlorine-releasing agent, up to about 3% of a ger-micide and up to about3% of a sodium silicate, the proportions being based on the weight ofthe dry ingredients, said composition providing an alkaline reaction inaqueous solution.

References Cited by the Examiner UNITED STATES PATENTS 2,634,240 4/1953Showalter ct al. 252138 XR 3,030,312 4/1962 Mills 252161 3,035,0545/1962 Symes et al 25299 XR 3,037,935 6/1962 Tidridge et al 252138 X3,064,048 11/1962 Schramrn et al. 252106 XR 3,066,104 11/1962 Dasch etal 252138 XR 3,134,711 5/l964 Reller et al 252106 XR LEON D. ROSDOL,Primary Examiner.

JULIUS GREENWALD, Examiner.

J. T. FEDIGAN, Assistant Examiner.

1. A COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 40% TO ABOUT 85% OF AWATER-SOLUBLE CONDENSED, INORGANIC POLYPHOSPHATE AND FROM ABOUT 15% TOABOUT 60% OF A WATER-SOLUBLE ARYL SULFONATE SELECTED FROM THE GROUPCONSISTING OF BENZENESULFONATE, ORTHO-XYLENESULFONATE,METAXYLENESULFONATE, PAPA-XYLENESULFONATE, TOLUENESULFONATE,ETHYLBENZENESULFONATE, N-PROPYLBENZENESULFONATE,ISOPROPYLBENZENESULFONATE AND MIXTURES THEREOF, THE PROPORTIONS BEINGBASED ON THE WEIGHT OF THE DRY INGREDIENTS, SAID COMPOSITION PROVIDINGAN ALKALINE REACTION IN AQUEOUS SOLUTION.